Froth flotation process employing polyamino methyl phenols



rates This application is a division of our copending application Serial No. 28,514, filed May 12, 1960, which latter application is a continuation-in-part of our copending application Serial No. 730,510, filed April 24, 1958. See also our copending application Serial No. 799,487, filed March 16, 1959, now abandoned, which is a division of Serial No. 730,510. This invention relates to a froth flotation process employing as a collector a compound which is (1) oxyalkylated, (2) acylated, (3) oxyalkylated then acylated, (4) acylated then oxyalkylated, and (5) acylated, then oxyalkylated and then acylated, monomeric polyaminomethyl phenols. These substituted phenols are produced by a process which is characterized by reacting a preformed methylol phenol (i.e. formed prior to the addition of the polyamine) with at least one mole of a secondary polyamine per equivalent of methylol group on the phenol, in the absence of an extraneous catalyst (in the case of an aqueous reaction mixture, the pH of the reaction mixture being determined solely by the methylol phenol and the secondary polyamine), until about one mole of water per equivalent of methylol group is removed; and then reacting this product with (1) an oxyalkylating agent, (2) an acylating agent, (3) an oxyalkylating agent then an acylating agent, (4) an acylating agent then an oxyalkylating agent or (5) an acylating agent then an oxyalkylating agent and then an acylating agent.

The reasons for the unexpected monomeric form and properties of the polyaminomethyl phenol are not understood. However, we have discovered that when (1) A preformed methylolphenol (i.e. formed prior to the addition of the polyamine) employed as a starting material is reacted with (2) A polyamine which contains at least one secondary amino group (3) In amounts of at least one mole of secondary polyamine per equivalent of methylol group on the phenol,

(4) In the absence of an extraneous catalyst, until (5) About one mole of water per equivalent of methylol group is removed, then Unite a monomeric polyaminomethyl phenol is produced which is capable of being oxyalkylated, acylated, oxyalkylated then acylated, or acylated then oxyalkylated, or acylated, then oxyalkylated and then acylated to provide the superior products employed in the process of this invention. All of the above five conditions are critical for the production of these monomeric polyaminomethyl phenols.

In contrast, if the methylol phenol is not preformed but is formed in the presence of the polyamine, or the preformed methylol phenol is condensed with the polyamine in the presence of an extraneous catalyst, either acidic or basic, for example, basic or alkaline materials such as NaOH, Ca(OH) Na CO sodium methylate, etc., a polymeric product is formed. Thus, if an alkali metal phenate is employed in place of the free phenol, or even if a lesser quantity of alkali metal is present than is required to form the phenate, a polymeric product is formed. Where a polyamine containing only primary amino groups and no secondary amino groups is reacted with a methylol phenol, a polymeric product is also produced. Similarly, where less than one mole of secondary atent fire amine is reacted per equivalent of methylol group, a polymeric product is also formed.

in general, the monomeric polyaminornethyl phenols are prepared by condensing the methylol phenol with the secondary amine as disclosed above, said condensation being conducted at a temperature sufiiciently high to eliminate water but below the pyrolytic point of the reactants and product, for example, at to 200 C., but preferably at to C. During the course of the condensation water can be removed by any suitable means, for example, by use of an azeotroping agent, reduced pressure, combinations thereof, etc. Measuring the water given off during the reaction is a convenient method of judging completion of the reaction.

The classes of methylol phenols employed in the condensation are as follows:

M0n0plzen0ls.-A phenol containing 1, 2 or 3 methylol groups in the ortho or para position (i.e. the 2, 4, 6 positions), the remaining positions on the ring containing hydrogen or groups which do not interfere with the polyamine-methylol group condensation, for example, alkyl, alkenyl, cycloalkyl, phenyl, halogen, and alkoxy, etc., groups, and having but one nuclear linked hydroxyl group.

Diphenols.0ne type is a diphenol containing two hydroxybenzene radicals directly joined together through the ortho or para (i.e. 2, 4, or 6) position with a bond joining the carbon of one ring with the carbon of the other ring, each hydroxybenzene radical containing 1 to 2 methylol groups in the 2, 4 or 6 positions, the remaining positions on each ring containing hydrogen or groups which do not interfere with the polyamine-methylol group condensation, for example, alkyl, alkenyl, cycloalkyl, phenyl, halogen, alkoxy, etc., groups, and having but two nuclear linked hydroxyl groups.

A second type is a diphenol containing two hydroxybenzene radicals joined together through the ortho or para (i.e. 2, 4, or 6 position) with a bridge joining the carbon of one ring to a carbon of the other ring, said bridge being, for example, alkylene, alkylidene, oxygen, carbonyl, sulfur, sulfoxide and sulfone, etc., each hydroxybenzene radical containing 1 to 2 methylol groups in the 2, 4, or 6 positions, the remaining positions on each ring containing hydrogen or groups which do not interfere with the polyaminomethylol group condensation, for example, alkyl, alkenyl, cycloalkyl, phenyl, halogen, alkoxy, etc., groups, and having but two nuclear linked hydroxyl groups.

The secondary polyamines employed in producing the condensate are illustrated by the following general formula: R

where at least one of the Rs contains an amino group and the Rs contain alkyl, alkoxy, cycloalkyl, aryl, ar alkyl, alkaryl radicals, and the corresponding radicals containing heterocyclic radicals, hydroxy radicals, etc. The Rs may also be joined together to form heterocyclic polyamines. The preferred classes of polyamines are the alkylene polyamines, the hydroxylated alkylene polyamines, branched polyamines containing at least three primary amino groups, and polyamines containing cyclic amidine groups. The only limitation is that there shall be present in the polyamine at least one secondary amino group which is not bonded directly to a negative radical which reduces the basicity of the amine, such as a phenyl group.

An unusual feature of the products employed in the process of the present invention is the discovery that methylol phenols react more readily under the herein specified conditions with secondary amino groups than with primary amino groups. Thus, where both primary and secondary amino groups are present in the same molecule, reaction occurs more readily with the secondary amino group. However, where the polyamine contains only primary amino groups, the product formed under reaction conditions as mentioned above is an insoluble resin. In contrast, where the same number of primary amino groups are present on the amine in addition to at least one secondary amino group, reaction occurs predominantly with the secondary amino group to form non-resinous derivatives. Thus, where trimethylol phenol is reacted with ethylene diamine, an insoluble resinous composition is produced. However, where diethylene triamine, a compound having just as many primary amino groups as ethylene diamine, is reacted, according to this invention a non-resinous product is unexpectedly formed.

The term momomeric as employed in the specification and claims refers to a polyaminomethylphenol containing within the molecular unit one aromatic unit corresponding to the aromatic unit derived from the starting methylol phenol and one polyamine unit for each methylol group originally in the phenol. This is in contrast to a polymeric or resinous polyaminomethyl phenol containing within the molecular unit more than one aromatic unit and/or more than one polyamino unit for each methylol group.

The monomeric products produced by the condensation of the methylol phenol and the secondary amine may be illustrated by the following idealized formula:

where A is the aromatic unit corresponding to that of the methylol reactant, and the remainder of the molecule is the polyaminomethyl radical, one for each of the original methylol groups.

This condensation reaction may be followed by oxyalkylation in the conventional manner, for example, by means of an alpha-beta alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, octylene oxide, a higher alkylene oxide, styrene oxide, glycide, methylglycide, etc., or combinations thereof. Depending on the particular application desired, one may combine a large proportion of alkylene oxide, particularly ethylene oxide, propylene oxide, a combination or alternate additions or propylene oxide and ethylene oxide, or smaller proportions thereof in relation to the methylol phenol-amine condensation product. Thus, the molar ratio of alkylene oxide to amine condensate can range within wide limits, for example, from a 1:1 mole ratio to a ratio of 100021, or higher, but preferably 1 to 200. By proper control, desired hydrophilic or hydrophobic properties are imparted to the composition. As is well known, oxyalkylation reactions are conducted under a wide variety of conditions, at low or high pressures, at low or high temperatures, in the presence or absence of catalyst, solvent, etc. For instance oxyalkylation reactions can be carried out at temperatures of from 80200= C., and pressures of from to 200 p.s.i., and times of from min. to several days. Preferably oxyalkylation reactions are carried out at 80 to 120 C. and 10 to 30 p.s.i. For conditions of oxyalkylation reactions see U.S. Patent 2,792,369 and other patents mentioned therein.

As in the amine condensation, acylation is conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and the reaction products. In general, the reaction is carried out at a temperature of from 140 to 280 C., but preferably at 140 to 200 C. In acylating, one should control the reaction so that the phenolic hydroxyls are not acylated. Because acyl halides and anhydrides are capable of reacting with phenolic hydrolysis, this type of acylation should be avoided. It should be realized that either oxyalkylation or acylation can be employed alone or each alternately, either one preceding the other. In addition, the amine condensate can be acylated, then oxyalkylated and then reacylated. The amount of acylation agent reacted will depend on reactive groups or the compounds and propertie desired in the final product, for example, the molar ratios of acylation agent toamine condensate can range from 1 to 15, or higher, but preferably l to 4.

Where the above amine condensates are treated with alkylene oxides, the product formed will depend on many factors, for example, whether the amine employed is hydroxylated, etc. Where the amines employed are nonhydroxylated, the amine condensate is at least susceptible to oxyalkylation through the phenolic hydroxyl radical. Although the polyamine is non-hydroxylated, it may have one or more primary or secondary amino groups which may be oxyalkylated, for example, in the case of tetraethylene pentamine. Such groups may or may not be susceptible to oxyalkylation for reasons which are obscure. Where the non-hydroxylated amine contains a plurality of secondary amino groups, wherein one or more is susceptible to oxyalkylation, or primary amino groups, oxyalkylation may occur in those positions. Thus, in the case of the non-hydroxylated polyamines oxyalkylation may take place not only at the phenolic hydroxyl group but also at one or more of the available amino groups. Where the amine condensate is hydroxyalkylated, this latter group furnishes an additional position of oxyalkylation susceptibility.

The product formed in acylation will vary with the particular polyaminomethyl phenol employed. It may be an ester or an amide depending on the available reactive groups. If, however, after forming the amide at a temperature between -250 C., but usually not above 200 C., one heats such products at a higher range, approximately 250280 C., or higher, possibly up to 300 C. for a suitable period of time, for example, l-2 hours or longer, one can in many cases recover a second mole of water for each mole of carboxylic acid employed, the first mole of water being evolved during amidification. The product formed in such cases is believed to contain a cyclic amidine ring such as an imidazoline or a tetrahydropyrimidine ring.

Ordinarily the methods employed for the production of amino imidazolines result in the formation of substantial amounts of other products such as amido imidazolines. However, certain procedures are well known by which the yield of amino imidazolines is comparatively high as, for example, by the use of a polyamine in which one of the terminal hydrogen atoms has been replaced by a low molal alkyl group or an hydroxyalkyl group, and by the use of salts in which the polyamine has been converted into a monosalt such as combination with hydrochloric acid or paratoluene sulfonic acid. Other procedures involve reaction with a hydroxyalkyl ethylene diamine and further treatment of such imidazoline having a hydroxyalkyl substituent with two or more moles of ethylene imine. Other well known procedures may be employed to give comparatively high yields.

Other very useful derivatives comprise acid salts and quaternary salts, derived therefrom. Since the compositions contain basic nitrogen groups, they are capable of reacting with inorganic acids, for example hydrohalogens (HCl, HBr, HI), sulfuric acid, phosphoric acid, etc., aliphatic acids (acetic, propionic, glycolic, diglycolic, etc.) aromatic acids (benzoic, salicylic, phthalic, etc.), and organic compounds capable of forming salts, for example, those having the general formula RX wherein R is an organic group, such as an alkyl group (e.g. methyl, ethyl, propyl, butyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, pentadecyl, oleyl, octadecyl, etc.), cycloalkyl (e.g. cyclopentyl, cyclohexyl, etc.), aralkyl (e.g. benzyl, etc.), aralkyl (e.g. benzyl, etc.), and

the like, and X is a radical capable of forming a salt such as those derived from acids (e.g. halide, sulfate, phosphate, sulfonate, etc., radicals). The preparation of these salts and quaternary compounds is well known to the chemical art. For example, they may be prepared by adding suitable acids (for example, any of those mentioned herein as acylating agents) to solutions of the basic composition or by heating such compounds as alkyl halides with these compositions. Diacid and quaternary salts can also be formed by reacting alkylene dihalides, polyacids, etc. The number of moles of acid and quaternary compounds that may react with the composition of this invention will, of course, depend on the number of basic nitrogen groups in the molecule. These salts may be represented by the general formula N+X, wherein N comprises the part of the compound containing the nitrogen group which has been rendered positively charged by the H or R of the alkylating compound and X represents the anion derived from the alkylating compound.

THE METHYLOL PHENOL As previously stated, the methylol phenols include monophenols and diphenols. The methylol groups on the phenol are either in one or two ortho positions or in the para position of the phenolic rings. The remaining phenolic ring positions are either unsubstituted or substituted with groups not interfering with the amine methylol condensation. Thus, the monophenols have 1, 2 or 3 methylol groups and the diphenols contain 1, 2, 3 or 4 methylol groups.

The following is the monophenol most advantageously employed:

HO OH:- GHZOH This compound, 2,4,6-trimethylol phenol (TMP) is available commercially in 70% aqueous solutions. The designation TMP is sometimes used to designate trimethylol propane. Apparently no confusion is involved, in light of the obvious differences.

A second monophenol which can be advantageously employed is:

HO CH2- CHzOH where R is an aliphatic saturated or unsaturated hydrocarbon having, for example, 1-30 carbon atoms, for example, methyl, ethyl, propyl, butyl, sec-butyl, tert-butyl, amyl, tert-amyl, hexyl, tert-hexyl, octyl, nonyl, decyl, dodecyl, octo-decyl, etc., the corresponding unsaturated groups, etc.

The third monophenol advantageously employed is:

HOOHz- OHzOH OHaOH where R comprises an aliphatic saturated or unsaturated 6. hydrocarbon as stated above in the second monophenol, for example, that derived from cardanol or hydrocardanol.

The following are diphenol species advantageously employed:

One species is OHzOH R OHzOH where R is hydrogen or a lower alkyl, preferably methyl.

A second species is on on R! i no on? o- CHQOH R! where R has the same meaning as that of the second species of the monophenols and R is hydrogen or a lower alkyl, preferably methyl.

We can employ a wide variety of methylol phenols in the reaction, and the reaction appears to be generally applicable to the classes of phenols heretofore specified. Examples of suitable methylol phenols include- Monophenols:

Z-methylol phenol 2,6-dimethylol, 4-methyl phenol 2,4,6-trimethylol phenol 2,6-dimethylol, 4-cyclohexyl phenol 2,6'dimethylol-4-phenyl phenol 2,6-dimethylol-4-methoxyphenol 2,6-dimethylol-4-chlorophenol 2,6-dimethylol-3-methylphenol 2,6-dimethylol-4-sec-butylphenol 2,6-dimethylol,3,5-dimethyl-4-chlorophenol 2,4,6-trimethylol,3-pentadecyl phenol 2,4,6-trimethylo1,3-pentadecadienyl phenol H1011 HzQH on on noonfiom-Oomon C 20H CflIaOH OH OH HO OH UHF CHiOH H OH HOOHr- CHnOH JJH:

HaQH lHzOH OH CH HO-OHz CHzOH (5H CHzOH. CHzOH I CH3 H0 OH I a (j: CHzOH H2011 OHBOH CHZOH HO 3- OH CHzOH 0 0112011 HO-- OH ClihOH HzOH 0 on no CHz-O ..-[P-ora0n ln is 12H Examples of additional methylol phenols which can be employed to give the useful products of this invention are described in The Chemistry of Phenolic Resins, by Robert W. Martin, Tables V and VI, pp. 32-39 (Wiley, 1956).

THE POLYAMINE As noted previously, the general formula for the polyamine is This indicates that a wide variety of reactive secondary polyamines can be employed, including aliphatic polyamines, cycloaliphatic polyamines, aromatic polyamines (provided the aromatic polyamine has at least one secondary amine which has no negative group, such as a phenyl group directly bonded thereto) heterocyclic polyamines and polyamines containing mixtures of the above groups. Thus, the term polyamine includes compounds having one amino group on one kind of radical, for example, an aliphatic radical, and another amino group on the heterocyclic radical as in the case of the fol. lowing formula:

N-OHz u o- N-CH: C2HAOH provided, of course, the polyamine has at least one secondary amino group capable of condensing with the methylol group. It also includes compounds which are totally heterocyclic, having a similarly reactive secondary amino group. It also includes polyamines having other elements besides carbon, hydrogen and nitrogen, for example, those also containing oxygen, sulfur, etc. As previously stated, the preferred embodiments of the present invention are the alkylene polyamines, the hydroxylated alkylene polyamines and the amino cyclic amidines.

Polyamines are available commercially and can be prepared by well-known methods. It is Well known that olefin dichlorides, particularly those containing from 2 to 10 carbon atoms, can be reacted with ammonia or amines to give alkaylene polyamines. If, instead of using ethylene dichloride, the corresponding propylene, butylene, amylene or higher molecular weight dichlorides are used, one then obtains the comparable homologues. One can also use alpha-omega dialkyl ethers such as ClCH CH OCH CI-I Cl, and the like. Such polyamines can be alkylated in the manner commonly employed for alkylating monoamines. Such alkylation results in products which are symmetrically or non-symmetrically alkylated. The symmetrically alkylated polyamines are most readily obtainable. For instance, alkylated products can be derived by reaction between alkyl chlorides, such as propyl chloride, butyl chloride, arnyl chloride, cetyl chloride, and the like and a polyamine having one or more primary amino groups. Such reactions result in the formation of hydrochloric acid, and hence the resultant product is an amine hydrochloride. Th conventional method for conversion into the base is to treat with dilute caustic solution. Alkylation is not limited to the introduction of an alkyl group, but as a matter of fact, the radical introduced can be characterized by a carbon atom chain interrupted at least once by an oxygen atom. In other words, alkylation is accomplished by compounds which are essentially alkyoxyalkyl chlorides, as, for example, the following:

The reaction involving the alkylene dichlorides is not limited to ammonia, but also involves amines, such as ethylamine, propy-lam-ine, butylamine, octylamine, decylamine, cetylamine, dodecylamine, etc. Cycloaliphatic and aromatic amines are also reactive. Similarly, the reaction also involves the comparable secondary amines, in which various alkyl radicals previously mentioned appear twice and are types in which two dissimilar radicals appear, for instance, amyl butylamine, hexyl octylamine, etc. Furthermore, compounds derived by reactions involving alkylene dichlorides and a mixture of ammonia and amines, or a mixture of two different amines are useful. However, one need not employ a polyamine having an alkyl radical. For instance, any suitable polyalkylene polyamine, such as an ethylene polyamine, a propylene polyamine, etc., treated with ethylene oxide or similar oxyalkylating agent are useful. Furthermore, various hydroxylated amines, such as monoethanolamine, monopropanolamine, and the like, are also treated with a suitabl alkylene dichloride, such as ethylene dichloride, propylene dichloride, etc.

As to the introduction of a hydroxylated group, one can use any one of a number of well-known procedures such as alkylation, involving a chlorhydrin, such as ethylene chlorhydrin, glycerol chlorhydrin, or the like. Such reactions are entirely comparable to the alkylation reaction involving alkyl chlorides previously described. Other reactions involve the use of an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, octylene oxide, styrene oxide or the like. Glycide is advantageously employed. The type of reaction just referred to is Well known and results in the introduction of a hydroxylated or polyhydroxylated radical in an amino hydrogen position. It is also possible to introduce a hydroxylated oxyhydrocarbon atom; for instance, instead of using the chlorhydrin corresponding to ethylene glycol, one employs the chlorhydrin corresponding to diethylene glycol. Similarly, instead of using the chlorhydrin corresponding to glycerol, one employs the chlorhydrin corresponding to diglycerol.

From the above description it can be seen that many of the above polyamines can be characterized by th general formula R x R where the Rs, which are the same or different, comprise hydrogen, alkyl, cycloalkyl, aryl, alkyloxyalkyl, hydroxylated alkyl, hydroxylated alkyloxyalkyl, etc., radicals, x is zero or a whole number of at least one, for example 1 to 10, but preferably 1 to 3, provided the polyamine contains at least one secondary amino group, and n is a Whole number, 2 or greater, for example 2-10, but preferably 2-5. Of course, it should be realized that the amino or hydroxyl group may be modified by acylation to form amides, esters or mixtures thereof, prior to the methylol-amino condensation provided at least one active secondary amine group remains on the molecule. Any of the suitable acylating agents herein described may be employed in this acylation. Prior acylation of the amine can advantageously be used instead of acylation subsequent to amine condensation.

A particularly useful class of polyamines is a class of branched polyamines. These branched polyamines are polyalkylene polyamines wherein the branched group is a side chain containing on the average at least one nitrogen-bonded aminoalkylene group per nine amino units present on the main chain, for example 1-4 of such branched chains per nine units on the main chain, but preferably one side chain unit per nine main chain units. Thus, these polyamines contain at least three primary amino groups and at least one tertiary amino group in addition to at least one secondary amino group.

These branched polyamines may be expressed by the formula l t... l.

Where n is an integer, for example 1-20 or more but preferably 1-3, wherein R is preferably ethylene, but may be propylene, butylene, etc. (straight chained or branched).

The particularly preferred branched polyamines are presented by the following formula:

The radicals in the brackets may be joined in a headto-head or a head-to-tail fashion. Compounds described by this formula wherein n=1-3 are manufactured and sold by Dow Chemical Company as Polyamines N-400, N- 800, N-l200, etc. Polyamine N-400 has the above formula wherein n=1 and was the branched polyarnine employed in all of the specific examples.

The branched polyamines can be prepared by a Wide variety of methods. One method comprises the reaction of ethanolamine and ammonia under pressure over a fixed bed of a metal hydrogenation catalyst. By controlling the conditions of this reaction one can obtain various amounts of piperazine and polyamines as well as the branched chain polyalkylene polyamine. This process is described in Australian Patent No. 42,189 and in the East German Patent 14,480 (March 17, 1958) reported in Chem. Abstracts, August 10, 1958, 14129.

The branched polyamines can also be prepared by the following reactions:

'Iriethylene tetramine 1 OH: R

I H: NH:

N-CHZ-OHT-NHZ Suitable polyamines also include polyamines wherein the alkylene group or groups are interrupted by an oxygen radical, for example,

R R R R X R or mixtures of these groups and alkylene groups, for example,

R R R R /x R where R, n and x has the meaning previously stated for the linear polyamine.

For convenience the aliphatic polyamines have been classified as nonhydroxylated and hydroxylated alkylene polyamino amines. The following are representative members of the nonhydroxylated series:

Diethylen triamine,

Dipropylen triamine,

Dibutylene tn'arnine, etc.

Triethylene tetramine,

Tripropylene tetramine,

Tributylene tetramine, etc.,

Tetraethylene pentamine,

Tetrapropylene pentamine,

Tetrabutylene pentamine, etc.,

Mixtures of the above,

Mixed ethylene, propylene, and/or butylene, etc., polyamines and other members of the series.

The above polyamines modified with higher molecular weight aliphatic groups, for example, those having from 830 or more carbon atoms, a typical example of which is where the aliphatic group is derived from any suitable source, for example, from compounds of animal or vegetable origin, such as coconut oil, tallow, tall oil, soya, etc., are Very useful. In addition, the polyamine can contain other akylene groups, fewer amino groups, additional higher aliphatic groups, etc., provided the polyamine has at least one reactive secondary amino group.

N Hg

Compositions of this type are described in U.S. Patent 2,267,205.

Other useful aliphatic polyamines are those containing substituted groups on the chain, for example, aromatic groups, heterocyclic groups, etc., such as a compound of the formula where R is alkyl and Z is an alkylene group containing phenyl groups on some of the alkylene radicals since the phenyl group is not attached directly to the secondary amino group.

In addition, the alkylene group substituted with a hydroxy group is reactive.

Polyamines containing aromatic groups in the main part of the chain are useful, for example, N,N-dimethylp-xylylenediamine.

Examples of polyamines containing solely secondary amino groups include the following:

Examples of polyamines having hydro-xylated groups include the following:

N C2H4NC2H4N H CzHs Suitable cyclic amidines include 1 4 4-methyl,2-dodecyl,1 methylaminoethylannnoethyl tetrahydropyrimidine N-CH2 ogHiN As previously stated, there must be reacted at least one mole of polyamine per equivalent of methylol group. The upper limit to the amount of amine present, will be determined by convenience and economics, for example, 1 or more moles of polyamine per equivalent of methylol group can be employed.

The following examples are illustrative of the preparation of the polyaminomethylol phenol condensate and are not intended for purposes of limitation.

The following general procedure is employed in preparing the polyamine-methylol condensate. The methylolphenol is generally mixed or slowly added to the polyamine in ratios of mole of polyamine per equivalent of methylol group on the phenol. However, where the polyamine is added to the methylolphenol, addition is carried out below 60 C. until at least one mole of polyamine per methylol group has been added. Enough of a suitable azeotroping agent is then added to remove water (benzene, toluene, or xylene) and heat applied. After removal of the calculated amount of water from the reaction mixture (one mole of water per equivalent of methylol group) heating is stopped and the azeotroping agent is evaporated off under vacuum. Although the reaction takes place at room temperature, higher temperatures are required to complete the reaction. Thus, the temperature during the reaction generally varies from -160 C. and the time from 424 hours. In general, the reaction can be efifected in the lower time range employing higher temperatures. However, the time test of completion of reaction is the amount of water removed.

Example 1 a This example illustrates the reaction of a methylolmonophenol and a polyamine. A liter flask is employed with a conventional stirring device, thermometer phase separating trap condenser, heating mantle, etc. 70% aqueous 2,4,6-trimethylol phenol which can be prepared by conventional procedures or purchased in the open market, in this instance, the latter, is employed. The amount used is one gram mole, i.e. 182 grams, of anhydrous trimethylol phenol in 82 grams of Water. This represents three equivalents of methylol groups. This solution is added dropwise with stirring to three gram moles (309 grams) of diethylene triamine dissolved in ml. of xylene over about 30 minutes. An exothermic reaction takes place at this point but the temperature is maintained below approximately 60 C. The temperature is then raised so that distillation takes place with the removal of the predetermined amount of Water, i.e., the Water of solution as Well as water of reaction. The water of reaction represents 3 gram moles or 54 grams.

The entire procedure including the initial addition of the trimethylol phenol until the end of the reaction is approximately 6 hours. At the end of the reaction period the xylene is removed, using a vacuum of approximately 80 mm. The resulting product is a viscous Water-soluble liquid of a dark red color.

Example 28a This example illustrates the reaction of a methylolmonophenol and a branched polyamine. A one liter flask is employed equipped with a conventional stirring device, thermometer, phase separating trap, condenser, heating mantle, etc. Polyamine N-400, 200 grams (0.50 mole), is placed in the flask and mixed with grams of xylene.

To this stirred mixture is added dropwise over a period of 15 minutes 44.0 grams (0.17 mole) of a 70% aqueous solution of 2,4,6-trimethylol phenol. There is no apparent temperature change. The reaction mixture is then heated to 140 C., refluxed 45 minutes, and 24 milliliters of water is collected (the calculated amount of water is 22 milliliters). The product is a dark brown liquid (as a 68% xylene solution).

Example 2d This example illustrates the reaction of a methylol diphenol.

One mol of substantially water-free CHzOH CHa CHzOH HO O -OH CHZOH CH CHZOH and 4 moles of triethylenetetramine in 300 ml. of xylene are mixed with stirring. Although an exothermic reaction takes place during the mixing, the temperature is maintained below 60 C. The reaction mixture is then heated and azeotroped until the calculated amount (72 g.) of water is removed (4 moles of water of reaction). The maximum temperature is 150 C. and the total reaction time is 8 hours. Xylene is then removed under vacuum. The product is a viscous water-soluble liquid.

Example 5b In this example, 1 mole of substantially water-free HOCH OHQOH is reacted with 2 moles of Duomeen S (Armour Co.),

where R is a fatty group derived from soya oil, in the manner of Example 2a. Xylene is used as both solvent and azeotroping agent. The reaction time is 8 hours and the maximum temperature 150l60 C.

Example 28b This experiment is carried out in the same equipment as is employed in Example 28a except that a 300 milliliter flask is used. Into the flask is placed 50 grams of xylene and 8.4 grams (0.05 mole) of 2,6-dimethylol-4-methylphenol are added. The resulting slurry is stirred and warmed up to 80 C. Polyamine N400, 40.0 grams (0.10 mole) is added slowly over a period of 45 minutes. Solution takes place upon the addition of the polyamine. The reaction mixture is refluxed for about 4 hours at 140 C. and 1.8 milliliters of water is collected, the calculated amount. The product, as a xylene solution, is a brown liquid.

Example 29b This experiment is carried out in the same equipment and in the same manner as is employed in Example 28b. To a slurry of 10.5 grams (0.05 mole) of 2,6-dimethylol- 4-tertiarybutylphenol in 50 grams of xylene, 40 grams (0.10 mole) of Polyamine N-400 are added all at once with stirring and the mixture is heated and refluxed at 140 C. for 4 hours with the collection of 1.6 milliliters of water. The calculated amount of water is 1.8 milliliters. The product, as a xylene solution, is reddish brown.

1 6 Example 30b This experiment is carried out in the same equipment and in the same manner as'is employed in Example 28b. To a slurry of 14.0 grams of 2,6-dimethylol-4-nonylphenol in 50 milliliters of benzene, 40.0 grams (0.10 mole) of Polyamine N-40O are added all at once with stirring and the mixture is heated and refluxed at C. for 6 hours with the collection of 1.8 milliliters of water. The calculated amount of water is 1.8 milliliters. The product, as a xylene solution, is dark brown.

The following amino-methylol condensates shown in Tables I-IV are prepared in the manner of Examples 1a, 2d, and 5b. In each case one mole of polyamine per equivalent of methylol group on the phenol is reacted and the reaction carried out until, taking into consideration the water originally present, about one mole of water is removed for each equivalent of methylol group present on the phenol.

The pH of the reaction mixture is determined solely by the reactants (i.e., no inorganic base, such as Ca(OH) NaOI-l, etc. or other extraneous catalyst is present). Examples 1a, 2d, and 5b are also shown in the tables. Attempts are made in the examples to employ commercially available materials where possible.

In the following tables the examples will be numbered by a method which will describe the nature of the product. The polyamine-methylol condensate will have a basic number, for example, 1a, 4b, 6c, 4d, wherein those in the A series are derived from TMP, the B series from DMP, the C series from trimethylol cardanol and side chain hydrogenated cardanol (i.e., hydrocardanol), and the d series from the tetramethylol diphenols. The basic number always refers to the same amino condensate. The symbol A before the basic number indicates that the polyamine had been acylated prior to condensation. The symbol A after the basic number indicates that acylation takes place after condensation.

A25a means that the 25a (amino condensate) was prepared from an amine which had been acylated prior to condensation. However, 10aA means that the condensate was acylated after condensation. The symbol 0 indicates oxyalkylation. Thus 10aAO indicates that the amine condensate 10a has been acylated (lflaA), followed by oxyalkylation. 10aAOA means that the same condensate, 10a, has been acylated (10aA), then oxyalkylated (10aAO) and then acylated. In other words, these symbols indicate both kind and order of treatment.

R derived from soya oil.

611 Duomeen T (Armour 00.).

R derived from tallow.

TABLE II-Continued Polyamine Tert-butyl Octadeoyl Tert-butyl Dodecyl Amine ODT (Monsanto).

N-(2-hydroxyethy1)-2 methyl-1,2 propanediamine. N-methyl ethylene diamine.

N ,N-dimethyl ethylene dialnine.

Hydroxyethyl ethylene diamine.

N ,N-dil1ydroxyethylethylene diamine.

N-methyl propylene diamine. N,N-dihyd1oxyethyl propylene diamine. N,N'-dihydr0xypropyl propylene diamine.

N-CH2 The products formed in the above Table II are dark viscous liquids. 65

TABLE III Ex. R derived from- Reaction of 10... Oardanol Diethylene triamine.

2c d0 Triethylene tetramine. HO OH CHzOH 3c... Hydrogenated Tetraethylene pentamine.

70 oardanol.

4c do Dipropylene triamine. R 5c do Duomeen S (Armour 00.).

HQOH R-N-OHaCHaCHgNH:

. 1 (Trrmethylol cardano and sgiyglriaillllzeshydrogenated cardanol) with R derived from soya on TABLE III-Continued [Molar ratio of the trimethylol cardalno to amino 1:3]

a; 12 TABLE IIIContinued TABLE IVCntinued Ex. R Polyamine Ex. B Polyamine 60... do Duomeen T (Armour (30.). m... d0 Oxyethylated amine ODT.

H CzHiOH R-N-CHzGHzCHgNHg H C nHzr-N-C 1H4NC gH N R derived from tallow. H H 70... Oardanol Oxyethylated Duomeen S.

N- (Z-hydroxyethyl) -2 -methyl 1,2 propane- OZHAOH diamine. H N-methyl ethylene diarnine. RNOHzCHzCH N Diethylene triamine.

\ Triethylene tetraun'ne.

H Tetraethylene pentamine.

Dipropylene triamine. 8c Hydrogenated Oxyethylated Duomeen T. Duorneen S (Armour 00.).

oardanol.

C2H4OH H H RNCHr CH1 OHBNHZ RNOH2CH2CH2N R derived from soya oil.

l8d do Duomene T (Armour 00.). 9c... Cardanol Amine ODT (Monsanto). H

H R'N GH2OH2CH2NH2 12 NC2 aNCiH4NH2 H R derived from tallow.

100.. Hydrogenated Oxyethylated amine ODT. 19L... ..do Oxyethylated Duomeen S.

cardanol. 2

H C2H4OH H CQHAOH C 2H25g-C 2H4N-C gHrN R-N 0 H2 C H: C H2N\ 110.. Cardanol N (2 hydroxyethyl) 2 methyl 1,2- 20L". do Oxyethylated Duorneen T propanediamine. 120.- Hydrogenated N-methyl ethylene diamine. CiHiOH cardanol. H

RNCH2CH2CH2N\ The products formed in the above Table III are dark, H ViSCOlls li UidS. l 2111---- do Amine ODT (Monsanto).

H TABLE IV C12 2a-NC2H4NC2HiHNg Reaction of H (EHZOH R OHflOH 22-.- do Oxyethylated amine ODT.

I I Cl2H25-N-C2H4N-O2H4N 0112011 011203 E H (Tetramethylol diphenol) with polyamine 23'1"" undo rg hydrOXyethyK 2 methyl 1 propane.

' a lalIllHB. [Molar ratio of tetramethylol diphcnol to polyamrne 1.4] Min" "HA0 Nfllethyl ethylene diamine.

Ex R polyamme The products formed in the above Table IV are dark,

viscous liquids. methylene triamin? THE ACYLATING AGENT Trrethylene tetramine. getraethylene pentamine. As in the reaction between the methylol phenol and gggggfg ggfigfthe secondary amine, acylation is also carried out under H dehydrating conditions, i.e., water is removed. Any of R N CH2CH2OHZNH2 the well-known methods of acylation can be employed. R d 1f For example, heat alone, heat and reduced. pressure, heat mmsoya in combination with an azeotroping agent, etc., are all 6d do Duorneen T (Armour 00.): satisfactory,

H A wide variety of acylating agents can be employed. RN0HQCH20EiNHi However, strong acylating agents such as acyl halides, or R derjvedfmm n acid :anhydrides should be avoided since they are capable I 7d "do oxyethylated Duomeen S of esterrf rng phenolic hydroxy groups, a feature which is undesirable. H 02134015 Although a wide variety of carboXylic acids produce IFDFCHECHZCHZN excellent products, in our experience monocarboxy acids 6:} having more than 6 carbon atoms and less than 40 carbon atoms give most advantageous products. The most com- Oxyethylated Dumas mon examples include the detergent forming acids, i.e., 0 mm; those acids which combine with alkalies to produce soap or soap-like bodies. The detergent-forming acids, in turn, 7O lnclude naturally-occurring fatty acids, resin acids, such H as abietic acid, naturally occurring petroleum acids, such 9d --do Amine ODT (Monsanto). as naphthenic acids, and carboxy acids, produced by the oxidation of petroleum. As will be subsequently indicated, there are other acids which have somewhat similar characteristics and are derived from somewhat difierent ace-ease 235 sources and are diflFerent in structure, but can be included in the broad generic term previously indicated.

Suitable acids include straight chain and branched chain, saturated and unsaturated, aliphatic, alicyclic, fatty, aromatic, hydroaromatic, and aralkyl acids, etc.

Examples of saturated aliphatic monocarboxylic acids are acetic, propionic, butyric, valeric, caproic, heptanoic, caprylic, nonanoic, capric, undecanoi'c, lauric, tridecanoic, myristic, pentadecanoic, palmitic, heptadecanoic, stearic, nonadecanoic, eicosanoic, heneicosanoic, docosanoic, tricosanoic, tetracosanoic, pentacosanoic, cerotic, heptacos anoic, montanic, nonacosanoic, melissi'c and the like.

Examples of ethylenic unsaturated aliphatic acids are acrylic, methacrylic, crotonic, anglic, teglic, the pentenoic acids, the hexenoic acids, for example, hydrosorbic acid, the heptenoic acids the octenoic acids, the nonenoic acids, the decenoic acids, for example, obtusilic acid, the undecenoic acids, the dodecenoic acids, for example, lauroleic, linderic, etc, the tridecenoic acids, the tetradecenoic acids, for example, myristoleic acid, the pentadecenoic acids, the hexadecenoic acids, for example, palmitoleic acid, the heptadecenoic acids, the octodecenoic acids, for example, petrosilenic acid, oleic acid, elardic acid, the nonadecenoic acids, for example, the eicosenoic acids, the docosenoic acids, for example, erucic acid, brassidic acid, cetoleic acid, the tetradosenic acids, and the like.

Examples of dienoic acids are the pentadienoic acids, the hexadienoic acids, for example, sorbic acid, the octadienoic acids, for example, linoleic, and the like.

Examples of the trienoic acids are the octadecatrienoic acids, for example, linolenic acid, eleostearic acid, pseudoeleostearic acid, and the like.

Carboxylic acids containing functional groups such as hydroxy groups can be employed. Hydroxy acids, particularly the alpha hydroxy acids include glycolic acid, lactic acid, the hydroxyvaleric acids, the hydroxy caproic acids, the hydroxyheptanoic acids, the hydroxy caprylic acids, the hydroxynonanoic acids, the hydroxycapric acids, the hydroxydecanoic acids, the hydroxy lauric acids, the hydroxy tridecanoic acids, the hydroxymyristic acids, the hydroxypentadecanoic acids, the hydroxypalmitic acids, the hydroxyhexadecanoic acids, the hydroxyheptadecanoic acids, the hydroxy stearic acids, the hydroxyoctadecenoic acids, for example, ricinoleic acid, ricinelardic acid, hydroxyoctadecynoic acids, 'for example, ricinstearolic acid, the hydroxyelcosanoic acids, for example, hydroxyarachidic acid, the hydroxydocosanoic acids, for example, hydroxybehenic acid, and the like.

Examples of acetylated hydroxyacids are ricinoleyl lactic acid, acetyl -ricino1eic acid, chloroacetyl ricinoleic acid, and the like.

Examples of the cyclic aliphatic carboxylic acids are those found in petroleum called naphthenic acids, hydnocarpic and chaulmoogric acids, cyclopentane carboxylic acids, cyclohexanecarboxylic acid, campholic a cid, fenchlolic acids, and the like.

Examples of aromatic monocar boxylic acids are benzoic acid, substituted benzoic acids, for example, the toluic acids, the xyleneic acids, alkoxy benzoic acid, phenyl benzoic acid, naphthalene carboxylic acid, and the like.

Mixed higher fatty acids derived from animal or vegetable sources, for example, lard, cocoanut oil, rapeseed oil, sesame oil, palm kernel oil, palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow, soyabean oil, peanut oil, castor oil, seal oils, whale oil, shark oil, and other fish oils, teaseed oil, partially or completely hydrogenated animal and vegetable oils are advantageously employed. Fatty and similar acids include those derived from various waxes, such as beeswax, spermaceti, montan wax, Japan wax, coccerin and carnauba wax. Such acids include carnaubic acid, cerotic acid, lacceric acid, montanic acid, psyl'lastearic acid, etc. One may also employ higher molecular weight carboxylic acids derived by oxidation and other methods, such as from parafiin wax, petroleum and similar hydrocarbons; resinic and hydroaromatic acids, such as hexahydrobenzoic acid, hydrogenated naphthoic, hydrogenated carboxy diphenyl, naphthenic, and abietic acid; Twitchell fatty acids, carboxydiphenyl pyridine carboxylic acid, blown oils, blown oil fatty acids and the like.

Other suitable acids include phenylstearic acid, benzoylnonylie acid, cetyloxybutyric acid, cetyloxyacetic acid, chlorstearic acid, etc.

Examples of the polycarboxylic acids are those of the aliphatic series, for example, oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, nonanedicarboxylic acid, decanedicarboxylic acids, undecanedicarboxylic acids, and the like.

Examples of unsaturated aliphatic polycarboxylic acids are fumaric, maleic, mesocenic, citraconic, glutonic, itaconic, muconic, aconitic acids, and the like.

Examples of aromatic polycarboxylic acids are phthalic, iscphthalic acids, terephthalic acids, substituted derivatives thereof (eg. alkyl, chloro, alkoxy, etc. derivatives), biphenyldicarboxylie acid, diphenylether dicarboxylic acids, diphenylsulfone :dicarboxylic acids and the like.

Higher aromatic polycarboxylic acids containing more that two carboxylic groups are hemimellitic, trimellitic, trimesic, mellophanic, prehnitic, pyromellitic acids, meliitic acid, and the like.

Other polycarboxylic acids are the dimeric, trimeric and polymeric acids, for example, dilinoleic, trilinoleic, and other polyacids sold by Emery Industries, and the like. Other polycarboxylic acids include those containing ether groups, for example, diglycolic acid. Mixtures of the above acids can be advantageously mployed.

In addition, acid precursors such as esters, glycerides, etc. can be employed in place of the free acid.

The moles of acylating agent reacted with the polyaminomethyl compound will depend on the number of acetylation reactive positions contained therein as well as the number of moles one wishes to incorporate into the molecule. We have advantageously reacted l to 15 moles of acylating agent per mole of polyaminophenol, but preferably 3 to 6 moles.

The following examples are illustrative of the preparation of the acylated polyaminomethyl phenol condensate.

The following general procedure is employed in acylating. The condensate is mixed with the desired ratio of acid and a suitable azeotroping agent is added. Heat is then applied. After the removal of th calculated amount of water (1 to 2 equivalents per mole of acid employed), heating is stopped and the azeotroping agent is evaporated under vacuum. The temperature during the reaction can vary from 200 C. (except where the formation of the cyclic amidine type structure is desired and the maximum temperature is generally 200280 C.). The times range from 4 to 24 hours. Here again, the true test of the degree of reaction is the amount of water removed.

Example 3aA In a 5 liter, 3 necked flask furnished with a stirring device, thermometer, phase separating trap, condenser and heating mantle, 697 grams of 3a (one mole of the TMP- tetraethylene pentamine reaction product) is dissolved in 600 ml. of xylene. 846 grams of oleic acid (3 moles) is added to the TMP-polyamine condensate with tirring in ten minutes. The reaction mixture was then heated gradually to about in half an hour and then held at about over a period of 3 hours until 54 grams (3 moles) of Water is collected in the side of the tube. The solvent is then removed with gentle heating under a reduced pressure of approximately 20 mm. The product is a dark brown viscous liquid with a nitrogen content of 14.5%.

Example 30A The prior example is repeated except that the final reaction temperature is maintained at 240 C. and 90 grams moles) of Water is removed instead of 54 grams. Infrared analysis of the product indicates the presence of a cyclic amidine ring.

Example 7aA The reaction product of Example 7a (TMP and oxyethylated Duomeen S) is reacted With palmitic acid in the manner of Example SaA. A xylene soluble product is formed.

The following examples of acylated polyarninomethyl phenol condensates are prepared in the manner of the above examples. The products obtained are dark viscous liquids.

Example 28aA Into a 300 milliliter flask, fitted With a stirring device, thermometer, phase separating trap, condenser and heating mantle, is placed a xylene solution of the product of Example 28a containing 98.0 grams (0.05 mole) of the reaction product of 2,4,6-trimethylolphenol and Polyamine N-400 and about 24 grams of xylene. To this solution i added with stirring 30.0 grams (0.15 mole) of lauric acid. The reaction mixture is heated for about one hour at a maximum reaction temperature of 190 C. and 6 milliliters of water are collected. The calculated amount of Water for imidazoline formation is 5.4 milliliters. The resulting product as an 88 percent xylene solution is a dark brown thick liquid.

Example 28bA Into a 300 milliliter flask, fitted with a stirring device, thermometer, phase separating trap, condenser and heating mantle is placed 21 Xylene solution of the product of Example 286 containing 35.0 grams (0.025 mole) of the reaction product of 2,6-dimethylol-4-methylphenol and Polyamine N-400 and about grams of xylene. To this solution is added with stirring 14.1 grams (0.05 mole) of oleic acid. The reaction mixture is heated at reflux for 4.5 hours at a maximum temperature of 183 C. and 1.0 milliliter of Water is collected, the calculated amount of Water for amide formation being 0.9 milliliter. The product is a dark burgundy liquid (as 70.5% xylene solution).

Example 2911A This experiment is performed in the same equipment and in the same manner as employed in Exampl 2812A. Into the flask is placed a xylene solution of the product of Example 296 containing 40.9 grams (0.025 mole) of the reaction product of 2,6-dimethylol-4-tertiarybutyl phenol and Polyamine N-400 and about 47 grams of xylene. To this solution is added with stirring 7.2 grams (0.05 mole) of octanoic acid. The reaction mixture is heated at reflux for 3.75 hours at a maximum temperature of 154 C. and 1.3 milliliters of Water is collected. The calculated amount of Water for amide formation is 0.9 milliliter. The product as a 49.82 percent xylene solution was brown.

Example 3012A This experiment is performed in the same manner and in the same equipment as is employed in Example 28bA. Into the flask is placed a xylene solution of the product of Example 30b containing 39.6 grams (0.025 mole) of the reaction product of 2,6-dimethylol-4-nonylphenol and Polyamine N400 and about 32 grams of xylene. To this solution is added With stirring 14.2 grams (0.05 mole) of stearic acid. The reaction mixture is heated at reflux for 4 hours at a maximum temperature of 160 C. and 1.0 milliliter of Water is collected. The calculated amount of water for amide formation is 0.9 milliliter. The product as a 62.5% xylene solution is a brown liquid.

TABLE V Acylated Products of Table I Grams of acid Grams of Example Acid used per water gram-mole of removed condensate 111A Oleir- 846 54 N onanoic 316 36 Ole 846 54 846 852 54 Laurie 600 54 Myristic 684 54 Palmitic- 768 54 Pronanm' 222 54 Dimerlc 1 1, 800 54 in 846 54 llr/A ..(l0 846 54 12aA Sunaptic acid 2 990 54 14 A Oleio 846 54 1, 536 108 846 54 1, 692 108 1, 692 108 846 54 180 54 in 4 Laurie. 600 120 1 Dilinoleic acid sold by Emery Industries. Also employed in examples of Tables VI, VII, and VIII. gzg lgzagihthenic acid sold by Sun Oil Company, average molecular weight TABLE VI Acylated Products of Table II Grams ofaeid Grams of Example Acid used per water gram-mole of removed condensate 568 36 564 36 800 72 120 36 456 36 512 36 Dimerie 1 1, 200 36 Oleio 564 36 9774 do 564 36 lObA Sunaptic acid 2 660 36 116A Ole 564 36 564 36 512 36 240 72 564 36 l, 128 72 564 36 564 36 400 36 564 40 288 52 306A Stearie 569 40 See Table V for footnotes.

TABLE VII Acylaied Products of Table III Grams of acid Grams of Example Acid used per water gram-mole of removed condensate 10A Oleic 564 36 20A Palmitic. 512 36 30A Lauric 800 72 40A Myristic 456 26 6cA Acetic 120 36 60A Dimeric 1 1, 200 36 7cA Oleic 564 36 80.4.. do 564 36 90A Sunaptic acid 2 660 36 A Oleio 564 36 IA do 564 36 A do 564 36 See Table V for footnotes.

TABLE VIII Acylatfll Products of Table III Grams of acid used per gram-mole of condensate Grams of water removed Example Acid See Table V for footnotes.

Reference has been made and reference will be continued to be made herein to oxyalkylation procedures. Such procedures are concerned with the use of monoepoxides and principally those available commercially at low cost, such as ethylene oxide, propylene oxide and butylene oxide, octylene oxide, styrene oxide, etc.

Oxyalkylation is well known. For purpose of brevlty reference is made to Parts 1 and 2 of U.S. Patent No. 2,792,371, dated May 14, 1957, to Dickson, in which particular attention is directed to the various patents which describe typical oxyalkylation procedure. Furthermore, manufacturers of alkylene oxides furnish extensive information as to the use of oxides. For example, see the technical bulletin entitled Ethylene Oxide which has been distributed by the Jefferson Chemical Company, Houston, Texas. Note also the extensive bibliography in this bulletin and the large number of patents which deal with oxyalkylation processes.

The following examples illustrate oxyalklation.

Example 1aAO The reaction vessel employed is a 4 liter stainless steel autoclave equipped with the usual devices for heating and heat control, a stirrer, inlet and outlet means, etc., which are conventional in this type of apparatus. The stirrer is operated at a speed of 250 r.p.m. Into the autoclave is charged 1230 grams (1 mole) of MA, and 500 grams of Xylene. The autoclave i sealed, swept with nitrogen, stirring started immediately, and heat applied. The temperature is allowed to rise to approximately 100 C. at which time the addition of ethylene oxide is started. Ethylene oxide is added continuously at such speed that it is absorbed by the reaction mixture as added. During the addition 132 grams (3 moles) of ethylene oxide is added over 2% hours at a temperature of 100 C. to 120 C. and a maximum pressure of 30 p.s.i.

Example 1aA0 The reaction mass of Example 1A0 is transferred to a larger autoclave (capacity 15 liters) similarly equipped. Without adding any more xylene the procedure is repeated so as to add another 264 grams (6 moles) of ethylene oxide under substantially the same operating conditions but requiring about 3 hours for the addition.

Example 1aA0 In a third step, another 264 grams (6 moles) of ethyls ease-9e ene oxide is added to the product of Example laAO The reaction slows up and requires approximately 6 hours, using the same operating temperatures and pressures.

Example 1aA0 At the end of the third step the autoclave is opened and 25 grams of sodium methylate is added, the autoclave is flushed out as before, and the fourth and final oxyalkylation is completed, using 1100 grams (25 moles) of ethylene oxide. The oxyalkylation is completed within 6 /2 hours, using the same temperature range and pressure as previously.

Example 1aAO The reaction vessel employed is the same as that used in Example laAO. Into the autoclave is charged 1230 g. (1 mole) of MA and 500 grams of xylene. The autoclave is sealed, swept with nitrogen, stirring is started immediately, and heat is applied. The temperature is allowed to rise to approximately C. at which time the addition of propylene oxide is started. Propylene oxide is added continuously at such speed that it is absorbed by the reaction mixture as added. During the addition 174 g. (3 moles) of propylene oxide are added over 2 /2 hours at a temperature of 100 to C. and a maximum pressure of 30 lbs. p.s.i.

Example 1aA0 The reaction mass of Example laAO is transferred to a larger autoclave (capacity 15 liters). The procedure is repeated so as to add another 174 g. (3 moles) of propylene oxide under substantially the same operating conditions but requiring about 3 hours for the addition.

Example MAO At the end of the second step (Example 1aAO the autoclave is opened, 25 g. of sodium methylate is added, and the autoclave is flushed out as before. Oxyallrylation is continued as before until another 522 g. (9 moles) of propylene oxide are added. 8 hours are required to complete the reaction.

The following examples of oxyalkylation are carried out in the manner of the examples described above. A catalyst is used in the case of oxyethylation after the initial 15 moles of ethylene oxide are added, while in the case of oxypropylation, the catalyst is used after the initial 6 moles of oxides are added. In the case of oxybutylation, oxyocttylation, oxystyrenation, etc. the catalyst is added at the beginning of the operation. in all cases the amount of catalyst is about 1% percent of the total reactant present. The oxides are added in the order given reading from the left to right. The results are presented in the following tables:

Example EtO PrO BuO Octylene oxide Styrene oxide TABLE X TABLE XIV The Owyalhylatecl Products of Table II The Omflated Products of Table VI Grams of Oxide Added per Gram Mole of Condensate Grams of Oxide Added per Mole of Acylated Product Example EtO PrO B110 Octylene Styrene Oxide oxlde Example EtO PrO BuO Octylene Styrene oxide oxide TABLE XV TABLE XI t The Ozvyalkylatecl Products of Table III OwyaZM/la ed pfyoducts of Table VI Grams of Oxide Added per Gram Mole of Condensate Grams of Oxide Added per Glam Mole 0f Acylated Product Example EtO PrO B110 Octylene Styre e Example EtO PrO BuO Octylene Styrene oxide oxide 66 Oxide TABLE XII The Owyalkylaterl Products of Table IV TABLE XVI Grams of Oxide Added per Gram Mole of Condensate The Owyalkylated Products of Table VII Gra s fO'd Addd e M1 fA it (1 Example EtO PrO BuO Oetylene Styrene m 0 X1 e e p r Gram 0 e 0 Cy ed Pro uct oxide oxide 40 Octylene Styrene Example EtO PrO BuO oxide oxide TAB LE XIII The Oayalkylated Products of Table V Grams of Oxide Added per Gram Mole of Condensate Since the oxyalkylated, and the acylated and oxyalkylated products have terminal hydroxy groups, they can Example tO Pro B octylene styrene be acylated. This step is carried out in the manner preoxlde oxide viously described for acylation. These examples are illustrative and not limiting.

Example JaOA One mole (919 grams) of 12.0 mixed With 846 grams (three moles) of oleic acid and 300 ml. Xylene. The reaction mixture is heated to about ISO- C. over a period of 2 hours until 54 grams (3 moles) of water are removed. Xylene is then removed under vacuum. The product 100A is xylene soluble.

Example IaAOA The process of the immediately previous example is repeated using laAO. The product laAOA is xylene s01- uble.

Additional examples are presented in the following tables. All of the products are dark, viscous liquids.

TABLE XVII The Acylated Products of Tables IX, X, XI, XII

Grams of acid per gram-mole of oxyalkylatcd product Grams water removed Example Acid TABLE XVIII The Acylated Products of Tables XIII, XIV, X V, XVI

Grams water removed Grams of acid per gram-mole of oxyalkylatcd product Example Acid HF-HHwi HV- HHHFHHH Oommocmoomoooomoooooomm idAOA.-.

FLOTATION AGENTS This phase of the invention relates to the use of the aforementioned compounds in separating minerals by froth flotation, and particularly to separating metallic minerals. minerals or ores into their more valuable and their less Valuable components, by means of a froth flotation operation to beneflciate ores, particularly of metallic minerals, by applying a specifically novel reagent in a froth flotation operation.

Froth flotation has become established as a highly useful method of recovering from ores and minerals the relatively small percentages of valuable components they contain. The general technique is to grind the ore or mineral to such a degree that the individual grains of the valuable components are broken free of the less valuable components or gangue; make a liquid mass of such finely ground ores, which mass or pulp usually contains a major proportion of Water and only a minor proportion of finely-ground ore; subject such pulp to the action of a highly specific chemical reagent in a flotation machine or flotation cell, in the presence of a large amount of air; and recover the valuable constituents of the ore from the mineralized froth which overflows from the flotation cell. Many variations of this basic procedure have been developed, including the use of different types of flotation cells, different procedures of combining individual operations into different flow sheets to float successively and separately a number of valuable components, etc. The chemical side of the operation has likewise been varied greatly They provide a novel process for separating to make such complex operations practicable. In addition to reagents adapted to collect the ore values in the froth (collectors), other reagents for improving the frothing characteristics of the flotation operation (frothers) or for selectively improving or retarding the flotation of individual members among the valuable components of the ore (activators or depressors) have been developed. The characteristics of the chemical reagents that have been used in the flotation operation differ greatly, until it may be said that a reagents flotation possibilities may best be determined by actual test in the process.

Our process relates to the use of the compositions of this invention as promoters or collectors, particularly in selecting acidic minerals from other ore constituents. For various reasons, including Viscosity, We prefer to employ our reagents in the form of solution in a suitable solvent. in some instances, Where the compounds are water soluble, water is selected as a solvent. Where the reagent is Water insoluble, various organic solvents are employed.

We prefer to use our compounds and a solvent in proportions of 1:4 and 4:1. In some instances, the best results have been obtained by the use of reagents comprising substantially equal proportions of such two ingredients. On the other hand, mixtures in the proportions of 1:9 or 9:1 have sometimes been most useful.

The solvent employed may be selected as desired. In some instances, crude petroleum oil itself is satisfactory; in other cases, gas oil, kerosene, gasoline, or other distillate is to be preferred. We prefer specifically to employ the petroleum distillate sold commercially as stove oil, as it appears to have, in addition to desirable properties as used in our reagent for floating minerals, certain desirable physical properties, i.e., it is relatively stable and nonvolatile, it is relatively limpid, and it is relatively nonflammable.

The flotation reagent contemplated for use in our process is prepared by simply mixing the compound of our invention and the solvent in the desired proportions. The reagent so compounded is used in the ordinary operating procedure of the flotation process.

In some instances, the components of the mixture are compatible and combine into a perfectly homogeneous liquid reagent. In other instances, they are more or less incompatible, and tend to separate or stratify into layers on quiescent standing. In instances where the ingredients are capable of making a homogeneous mixture, the reagent may be handled and used without difficulty. If a non-homogeneous mixture results when the desired proportions are employed, a number of expedients may be resorted to to obviate the difliculty. For example, since it is common to include the use of a frothing agent in many flotation operations, the collector which comprises our reagent may be homogenized by being combined with a mutual solubilizer in the form of the desired frother, e.g., cresylic acid, pine oil, terpineol, one of the alcohols manufactured and used for froth promotion, like the DuPont alcohol frothers, etc. If such mutual solubilizer is incorporated in or with the compounds and petroleum body, as above described, the resulting reagent is also contemplated by us for use in our process.

Another means of overcoming the non-homogeneity of some of the examples of the reagents contemplated by us is to homogenize the mixture mechanically, as by a beater or agitator, immediately before injecting it into the inineral pulp which is to be treated for the recovery of mineral values.

The reagents of the present invention are eflective promoters or collecting agents for acidic ore materials generally and said acidic materials may be either worthless gangue or valuable ore constituents. The most important use, however, is in connection with the froth flotation of silica from non-metallic ores in which the siliceous gangue may represent a much smaller proportion of the ore rather than metallic and sulfide ores in which the gangue usually represents the major proportion of the ore. Representative acidic ore materials are the feldspars, quartz, pyroxenes, the spinels, blotite, muscovite, clays, and the ike.

Although the present invention is not limited to the treatment of any particular ore materials, it has been found to be well suited for froth flotation of silica from phosphate rock, and this is a preferred embodiment of the invention. In the processes of removing silica from phosphate rock the conditions are such that practically complete removal of the silica must be accomplished in order to produce a salable phosphate material. It is therefore an advantage of this invention that our reagents not only effect satisfactory removal of the silica but are economical in amounts used. For example, the quantities of active compounds required range from 0.1 pound to 2.0 pounds or more, but preferably 0.2 to 1.5 pounds, per ton of ore depending upon the particular ore and the particular reagent. The invention is not, however, limited to the use of such quantities.

These reagents can also be used for the flotation of feldspar from quartz and for the flotation of mica from quartz and calcite.

The reagents of the present invention can be used alone or in mixtures with other promoters. They can likewise be used in conjunction with other cooperating materials such as conditioning reagents, activators, frothing reagents, depressing reagents, dispersing reagents, oily materials such as hydrocarbon oils, fatty acids or fatty acid esters.

The present reagents are also adaptable for use in any of the ordinary concentrating processes such as film flotation, tabling, and particularly in froth flotation operations. The ore concentrating processes employed will depend upon the particular type or kind of ore which is being processed. For example, in connection with phosphate rock, relatively coarse phosphate-bearing materials, for example 28 mesh or larger, can be economically concentrated by using these reagents in conjunction with other materials such as fuel oil or pine oil in a concentration process employing tables or film flotation. The less than 28 mesh phosphate rock material is best concentrated by means of froth flotation employing these improved silica promoters.

When the reagents of the present invention are employed as promoters in the froth flotation of silica from phosphate rock the conditions may be varied in accordance with procedures known to those skilled in the art. The reagent can be employed in the form of aqueous solutions, emulsions, mixtures, or solutions in organic solvents such as alcohol and the like. The reagents can be introduced into the ore pulp in the flotation cell without prior conditioning or they can be conditioned with the ore pulp prior to the actual concentration operation. They can also be stage fed into the flotation circuit.

Other improved phosphate flotation features which are known may be utilized in connection with the present invention.

While the above relates specifically to the flotation of silica from phosphate rock, the present invention is not limited to such operations and the reagents are useful in the treatment of various other types of ore materials wherein it is desirable to remove acidic minerals in the froth. For example, the reagents are useful in the treatment of rake sands from the tailings produced in cement plant operations. In this particular instance, the rake sands are treated by flotation to remove part of the alumina which is present in the form of mica and the removal of silica is not desirable. Our reagents are useful in such flotation operations. The reagent may also be used for the flotation of silica from iron ores containing magnetite, limonite and quartz, and in tests conducted on this type of ore, the rough tailing resulting from the flotation of silica containing both magnetite and limonite assayed much higher in iron than concentrates produced by the conventional soap flotation of the iron minerals.

Some 10 million tons of phosphate rock are produced annually from the Florida pebble phosphate deposits. Located principally in Polk and Hillsborough Counties, these marine deposits produce three-fourths of the U.S. supply of phosphate and about three-eighths of the world supply.

Such pebble phosphate, as mined by the conventional strip-mining methods, includes undesirably large proportions of non-phosphate minerals, principally siliceous and principally silica, which reduce the quality and the price of this large-tonnage, small-unit-value product. Extensive and costly ore-dressing plants have consequently been required to deliver a finished product of acceptable grade.

Among the procedures employed, and one which is almost universally used by the industry, is a two-stage or double flotation process. In the first stage (or rougher flotation circuit), washed phosphate rock having particle sizes usually between about 28- and about ISO-mesh is subjected to the action of a reagent conventionally com prising tall oil, fuel oil, and caustic soda. The concentrate delivered by such rougher circuit is a phosphate rock of grade higher than the original rock but which still contains too much silica and similar impurities to be of acceptable market grade.

The rougher concentrate is therefore de-oiled with dilute sulfuric acid to remove the tall-oil-soap-and-fueloil reagent and is thereafter subjected to flotation in a secondary or cleaner flotation circuit. The froth prod uct delivered from this secondary circuit is high in silica and similar impurities and is desirably low in phosphate values so that it can be thereafter discarded.

Our process is particularly applicable to such secondary or cleaner flotation circuit of such a conventional flota tion scheme. Our process may, of course, be applied to beneficiate a phosphate rock that has not been subjected to such preliminary rougher circuit flotation process.

Because our compounds are most advantageously used in conventional flotation plants in the phosphate rock industry, and in the secondary-circuit or cleaner-circuit section of such plants, it is not necessary here to describe in detail how they are used. Where they are employed, the operation of the plant is continued in normal fashion, the only change being the substitution of our compounds for the conventional reagents otherwise used.

For sake of completeness, the following brief example of their use is presented.

Example A typical Florida pebble phosphate rock is subjected to conventional pre-flotation treatment and sizing. That portion having a particle-size range of from about 28- to about ISO-mesh is processed through a conventional rougher flotation circuit employing the conventiontal tall oil, fuel oil, and caustic soda reagents to float a phosphate rock concentrate. The concentrate delivered from such rougher circuit contains 12-14% insoluble matter, after deoiling with dilute sulfuric acid and washing with water. In the consequent secondary flotation circuit compound 10-1 of the table below is used at a rate of about 0.85 pound per ton of rougher concentrate.

Aeration is started, additional water being added to the cell as required to maintain the proper level as the froth is continuously skimmed off. The collected overflow and tailings are analyzed. The overflow froth is high in silica and low in bone phosphate of lime while the tailings in the underflow are low in silica and high in bone phosphate of lime.

By employing this process with the agents listed below one obtains a phosphate of marketable grade. Separation of the bone phosphate of lime with these compounds is more eflicient than with the conventional agents.

FLOTATION COLLECTION AGENTS Ex. Weight of oxides No. H20 added to I (grams) Reactants (grams) eliminated 101-- 1a (439) plus lauric acid 54 None.

(600). 102 .do 72 Do. 103- 1a (439) plus oleic acid 54 Do.

(846). 104 do 72 Do. 105 2a (568) plus stearic acid 54 Do.

Do. PrO (174). Octylene oxide (384).

Do. d BuO (216). 1b (492) plus oleic acid None.

(1128). 10-12. d0 36 PrO (232). 1013.. 2b((6:63%)) plus stearic acid 36 D0.

11 10-14.. 3b( plus lauric acid 36 Octylene oxide (384). 10-15- .-d 36 PrO (232 1016.. 10 835) plus lauric acid 54 None. 10-17.. 1d plus lauric acid 72 Do.

1o-1s. 4a 5 52' plus lauric acid 72 PrO(232). 19. 13116323) plus oleic acid 72 Styrene oxide (260).

1 1020.. 16d (800) plus oleic acid 72 BuO (288).

I II

Ex. N H2O Weight of oxides Reactants (grams) elimiadded to I in alphanated betical order (grams) (grams) 10 21 28a (196 (A) PTO (58 10 22' 28a(1960)plus1auricacid 120 (A) PrO (116) (B) EtO 600 (1320). 3 28:10 (3054) plus stcaric 18 acid (284).

EtO (1980). 151:0 (2640).

0-27.. l028.. (1635) (M 550 (522) (B) EtO 10-29 2% (1635) plus oleic acid 18 EtO (1320).

282 1 30 29b0 (2655) plusoleicacid 18 -82 1031 291111011 1032 301) (1580) EtO (2200). 10-33 30b (1580)plusstearicacid 40 '09 1034 mice 40 (A) PrO (464) (B) EtO (1320). 1035.. SObAOA We claim:

1. An improvement in the beneficiation of ore containing siliceous material by means of a froth flotation process characterized by employing as a collector a member selected from the group consisting of:

(1) acylated, (2) oxyalkylated, (3) acylated then oxyalkylated, (4) oxyalkylated then acylated, (4) acylated, then oxyalkylated and then acylated, monomeric polyaminomethyl phenols characterized by reacting a preformed methylol phenol having one to four methylol groups in the 2,4,6-position with a polyamine containing at least one secondary amine group in amounts of at least one mole of secondary polyamine per equivalent of methylol group on the phenol until one mole of Water per equivalent of methylol group is removed, in the absence of an extraneous catalyst; and then reacting the thus formed monomeric polyaminomethyl phenol with a member selected from the group consisting of (1) an acylation agent, (2) an oxyalkylation agent, (3) an acylation then an oxyalkylation agent, (4) an oxyalkylation then an acylation agent, and (5) an acylation then an oxyalkylation and then an acylation agent the preformed methylol phenol having only functional groups selected from the class consisting of methylol groups and phenolic hydroxyl groups, the polyamine having only functional groups selected from the class consisting of primary amino groups, secondary amino groups and hydroxyl groups, the acylation agent having up to 40 carbon atoms and being selected from the class consisting of unsubstituted carboxylic acids, unsubstituted hydroxy carbcxylic acids, unsubstituted acylated hydroxy carboxylic acids, lower alkanol esters of unsubstituted carboxylic acids, glycerides of unsubstituted carboxylic acids, unsubstituted carboxylic acid chlorides and unsubstituted carboxylic acid anhydrides, and the oxyalkylation agent being selected from the class consisting of alpha-beta alkyleneoxides and styrene oxide.

2. The process of claim 1 where the preformed methylol phenol has all available ortho and para positions substituted with methylol groups.

3. The process of claim 1 where the polyamine is an aliphatic polyamine.

4. The process of claim 1 where the polyamine is a polyalkylene polyamine.

5. The process of claim 1 where the acylation agent is a monocarboxy acid having 7 to 39 carbon atoms.

6. The process of claim 1 where the oxyalkylation agent is at least one 1,2-alkylene oxide having 2 to 4 carbon atoms.

7. The process of claim 1 Where the preformed methylol phenol is 2,4,6-trimethylol phenol, the polyamine is a polyalkylene polyamine, the acylation agent is a monocarboxy acid having 7 to 39 carbon atoms, and the oxyalkylation agent is at least one 1,2-alkylene oxide.

8. The process of claim 1 where the member is an acylated monomeric polyaminomethyl phenol.

9. The process of claim 1 where the member is an acylated then oxyalkylated monomeric polyaminomethyl phenol.

10. The process of claim 8 where the preformed methylol phenol is 2,4,6-trimethylol phenol, the polyamine is a polyalkylene polyamine, and the acylation agent is a monocarboxy acid having 7 to 39 carbon atoms.

11. The process of claim 9 Where the preformed methylol phenol is 2,4,6-trimethylol phenol, the polyamine is a polyalkylene polyamine, the acylation agent is a monocarboxy acid having 7 to 39 carbon atoms, and the oxyalkylation agent is at least one 1,2-alkylene oxide.

12. The process of claim 10 where the preformed methylol phenol is 2,4,6-trimethylol phenol, the polyamine is diethylene triamine, and the acylation agent is oleic acid.

13. The process of claim 10 where the preformed methylol phenol is 2,4,6-trirnethylol phenol, the polyamine is diethylene triamine, and the acylation agent is stearic acid.

14. The process of claim 10 where the preformed methylol phenol is 2,4,6-trin1ethylol phenol, the polyamine is triethylene tetramine, and the acylation agent is stearic acid.

15. The process of claim 9 where the preformed methylol phenol is para dodecyl ortho dimethyl phenol, the polyamine is diethylene triamine, the acylation agent is oleic acid, and the oxyalkylation agent is at least one 1,2- alkylene oxide having 2 to 4 carbon atoms.

16. The process of claim 15 Where the 1,2-alkylene oxide is propylene oxide.

References Cited in the file of this patent UNITED STATES PATENTS 

1. AN IMPROVEMENT IN THE BENEFICIATION OF ORE CONTAINING SILICEOUS MATERIAL BY MEANS OF A FORTH FLOTATION PROCESS CHARACTERIZED BY EMPLOYING AS A COLLECTOR A MEMBER SELECTED FROM THE GROUP CONSISTING OF: (1) ACYLATED, (2) OXYALKYLATED, (3) ACYLATED THEN OXYALKYLATED, (4) OXYALKYLATED THEN ACYLATED, (4) ACYLATED, THEN OXYALKYLATED AND THEN ACYLATED, MONOMERIC POLYAMINOMETHYL PHENOLS CHARACTERIZED BY REACTING A PREFORMED METHYLOL PHENOL HAVING ONE TO FOUR METHYLOL GROUPS IN THE 2,4,6-POSITION WITH A POLYAMINE CONTAINING AT LEAST ONE SECONDARY AMINE GROUP IN AMOUNTS OF AT LEAST ONE MOLE OF SECONDARY POLYAMINE PER EQUIVALENT OF MEETHYLOL GROUP ON THE PHENOL UNTIL ONE MOLE OF WATER PER EQUIVALENT OF METHYLOL GROUP IS REMOVED, IN THE ABSENCE OF AN EXTRANEOUS CATALYST; AND THEN REACTING THE THUS FORMED MONOMERIC POLYAMINOMETHYL PHENOL WITH A MEMBER SELECTED FROM THE GROUP CONSISTING OF (1) AND ACYLATION AGENT, (2) AN OXYALKYLATION AGENT, (4) AND OXYALKYLATION THEN AN OXYALKYLATION AGENT, (3) AN ACYLATION THEN AN ACYLATION AGENT, AND (5) AN ACYLATION THEN AN OXYALKYLATION AND THEN ANACYLATION AGENT THE PERFORMED METHYLOL PHENOL HAVING ONLY FUNCTIONAL GROUPS SELECTED FROM THE CLASS CONSISTING OF METHYLOL GROUPS AND PHENOLIC HYDROXYL GROUPS, THE POLYAMINE HAVING ONLY FUNCTIONAL GROUPS SELECTED FROM THE CLASS CONSISTING OF PRIMARY AMINO GROUPS, SECONDARY AMINO GROUPS AND HYDROXYL GROUPS, THE ACYLATION AGENT HAVING UP TO 40 CARBON ATOMS AND BEING SELECTED FROM THE CLASS CONSISTING OF UNSUBSTITUTED CARBOXYLIC ACIDS, UNSUBSTITUTED HYDROXY CARBOXYLIC ACIDS, UNSUBSTITUTED ACYLATED HYDROXY CARBOXYLIC ACIDS, LOWER ALKANOL ESTERS OF UNSUBSTITUTED CARBOXYLIC ACIDS, GLYCERIDES OF UNSUBSTITUTED CARBOXYLIC ACIDS, UNSUBSTITUTED CARBOXYLIC BOXYLIC ACID CHLORIDES AND UNSUBSTITUTED CARBOXYLIC ACID ANHYDRIDES, AND THE OXYALKYLATION AGENT BEING SELECTED FROM THE CLASS CONSISTING OF ALPHA-BETA ALKYLENEOXIDES AND STYRENE OXIDE. 